Author, as appears in the article.: Poblet, JM; Luis Echegoyen; Ning Chen; Rodriguez-Fortea, A; Wenting Cai; Roser Morales-Martínez; Xingxing Zhang; Daniel Najera; Elkin L. Romero; Alejandro Metta-Magaña; Skye Fortier

Department: Química Física i Inorgànica

URV's Author/s: POBLET RIUS, JOSEP MARIA; Luis Echegoyen; Ning Chen; RODRÍGUEZ FORTEA, ANTONIO; Wenting Cai; Roser Morales-Martínez; Xingxing Zhang; Daniel Najera; Elkin L. Romero; Alejandro Metta-Magaña; Skye Fortier

Abstract: Charge transfer is a general phenomenon observed for all endohedral mono-metallofullerenes. Since the detection of the first endohedral metallofullerene (EMF), La@C82, in 1991, it has always been observed that the oxidation state of a given encapsulated metal is always the same, regardless of the cage size. No crystallographic data exist for any early actinide endohedrals and little is known about the oxidation states for the few compounds that have been reported. Here we report the X-ray structures of three uranium metallofullerenes, U@D3h-C74, U@C2(5)-C82 and U@C2v(9)-C82, and provide theoretical evidence for cage isomer dependent charge transfer states for U. Results from DFT calculations show that U@D3h-C74 and U@C2(5)-C82 have tetravalent electronic configurations corresponding to U4+@D3h-C744− and U4+@C2(5)-C824−. Surprisingly, the isomeric U@C2v(9)-C82 has a trivalent electronic configuration corresponding to U3+@C2v(9)-C823−. These are the first X-ray crystallographic structures of uranium EMFs and this is first observation of metal oxidation state dependence on carbon cage isomerism for mono-EMFs.

Research group: Química Quàntica

Thematic Areas: Química Química Chemistry

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 2041-6520

Author identifier: 0000-0002-4533-0623; ; ; 0000-0001-5884-5629; ; ; ; ; ; ;

Record's date: 2019-01-14

Last page: 5290

Journal volume: 8

Papper version: info:eu-repo/semantics/publishedVersion

Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2017/SC/C7SC01711A#!divAbstract

Article's DOI: 10.1039/c7sc01711a

Entity: Universitat Rovira i Virgili

Journal publication year: 2017

First page: 5282

Publication Type: Article Artículo Article